CN103521219B - Catalyst, the preparation method of the catalyst, the application of the catalyst - Google Patents
Catalyst, the preparation method of the catalyst, the application of the catalyst Download PDFInfo
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- CN103521219B CN103521219B CN201310280767.XA CN201310280767A CN103521219B CN 103521219 B CN103521219 B CN 103521219B CN 201310280767 A CN201310280767 A CN 201310280767A CN 103521219 B CN103521219 B CN 103521219B
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- precursor material
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- 239000003054 catalyst Substances 0.000 title claims abstract description 148
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 161
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims abstract description 87
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 78
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 54
- 230000003647 oxidation Effects 0.000 claims abstract description 53
- 239000012876 carrier material Substances 0.000 claims abstract description 49
- 239000010936 titanium Substances 0.000 claims abstract description 36
- 239000002245 particle Substances 0.000 claims abstract description 33
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 33
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000002105 nanoparticle Substances 0.000 claims abstract description 25
- 238000000576 coating method Methods 0.000 claims abstract description 15
- 239000000203 mixture Substances 0.000 claims abstract description 15
- 239000011248 coating agent Substances 0.000 claims abstract description 13
- 239000000463 material Substances 0.000 claims description 115
- 239000002243 precursor Substances 0.000 claims description 95
- 238000006243 chemical reaction Methods 0.000 claims description 60
- 238000000034 method Methods 0.000 claims description 40
- 235000013339 cereals Nutrition 0.000 claims description 35
- 238000000197 pyrolysis Methods 0.000 claims description 30
- -1 titanium halogen compound Chemical class 0.000 claims description 19
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 18
- 238000009434 installation Methods 0.000 claims description 18
- 239000001301 oxygen Substances 0.000 claims description 16
- 229910052760 oxygen Inorganic materials 0.000 claims description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 15
- 239000007789 gas Substances 0.000 claims description 15
- 230000003197 catalytic effect Effects 0.000 claims description 13
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- 229910044991 metal oxide Inorganic materials 0.000 claims description 11
- 230000001590 oxidative effect Effects 0.000 claims description 11
- 150000002941 palladium compounds Chemical class 0.000 claims description 11
- 150000004706 metal oxides Chemical class 0.000 claims description 9
- 229910052763 palladium Inorganic materials 0.000 claims description 9
- 239000010703 silicon Substances 0.000 claims description 9
- 229910052710 silicon Inorganic materials 0.000 claims description 9
- 239000003638 chemical reducing agent Substances 0.000 claims description 8
- 238000002485 combustion reaction Methods 0.000 claims description 8
- 239000007800 oxidant agent Substances 0.000 claims description 7
- 229910052721 tungsten Inorganic materials 0.000 claims description 7
- 239000010937 tungsten Substances 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 239000000470 constituent Substances 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 6
- 239000002912 waste gas Substances 0.000 claims description 6
- 150000003058 platinum compounds Chemical class 0.000 claims description 5
- 150000003377 silicon compounds Chemical class 0.000 claims description 5
- 150000003658 tungsten compounds Chemical class 0.000 claims description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- 150000003609 titanium compounds Chemical class 0.000 claims description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 3
- 229940045985 antineoplastic platinum compound Drugs 0.000 claims description 3
- 239000000919 ceramic Substances 0.000 claims description 3
- 229910000077 silane Inorganic materials 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- PXXRROSTRSLPET-UHFFFAOYSA-J C(C)(=O)[O-].[W+4].C(C)(=O)[O-].C(C)(=O)[O-].C(C)(=O)[O-] Chemical compound C(C)(=O)[O-].[W+4].C(C)(=O)[O-].C(C)(=O)[O-].C(C)(=O)[O-] PXXRROSTRSLPET-UHFFFAOYSA-J 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- 229910003910 SiCl4 Inorganic materials 0.000 claims description 2
- DCGQUTJLMIWWSV-UHFFFAOYSA-N [W].[N+](=O)(O)[O-] Chemical compound [W].[N+](=O)(O)[O-] DCGQUTJLMIWWSV-UHFFFAOYSA-N 0.000 claims description 2
- INNSZZHSFSFSGS-UHFFFAOYSA-N acetic acid;titanium Chemical compound [Ti].CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O INNSZZHSFSFSGS-UHFFFAOYSA-N 0.000 claims description 2
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical group C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 claims description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 2
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 claims description 2
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 claims description 2
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical group Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 claims 3
- 241000209094 Oryza Species 0.000 claims 2
- 235000007164 Oryza sativa Nutrition 0.000 claims 2
- 235000009566 rice Nutrition 0.000 claims 2
- 229910003074 TiCl4 Inorganic materials 0.000 claims 1
- CTUFHBVSYAEMLM-UHFFFAOYSA-N acetic acid;platinum Chemical compound [Pt].CC(O)=O.CC(O)=O CTUFHBVSYAEMLM-UHFFFAOYSA-N 0.000 claims 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims 1
- 239000003863 metallic catalyst Substances 0.000 claims 1
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical class [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 95
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 abstract description 9
- 239000004408 titanium dioxide Substances 0.000 description 29
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 25
- 238000007792 addition Methods 0.000 description 19
- 239000013078 crystal Substances 0.000 description 19
- 150000001875 compounds Chemical class 0.000 description 14
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 description 12
- 229910052799 carbon Inorganic materials 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 11
- 230000010718 Oxidation Activity Effects 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 239000004215 Carbon black (E152) Substances 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- 229910002091 carbon monoxide Inorganic materials 0.000 description 8
- 229930195733 hydrocarbon Natural products 0.000 description 8
- 150000002430 hydrocarbons Chemical class 0.000 description 8
- 230000008929 regeneration Effects 0.000 description 8
- 238000011069 regeneration method Methods 0.000 description 8
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 7
- 239000006229 carbon black Substances 0.000 description 7
- 238000010586 diagram Methods 0.000 description 7
- 238000005245 sintering Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 6
- 230000008901 benefit Effects 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 6
- 230000008859 change Effects 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 239000002159 nanocrystal Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 229910000765 intermetallic Inorganic materials 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- 230000006641 stabilisation Effects 0.000 description 4
- 238000011144 upstream manufacturing Methods 0.000 description 4
- 229910002089 NOx Inorganic materials 0.000 description 3
- 239000005864 Sulphur Substances 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000011105 stabilization Methods 0.000 description 3
- HBBATKAUXPHIQN-UHFFFAOYSA-N [Cl].[Ti] Chemical compound [Cl].[Ti] HBBATKAUXPHIQN-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 239000010721 machine oil Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 229910003446 platinum oxide Inorganic materials 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 230000008439 repair process Effects 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical group S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 2
- 229910001930 tungsten oxide Inorganic materials 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical class ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910019029 PtCl4 Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229910011009 Ti(NO3)2 Inorganic materials 0.000 description 1
- ZDYCQQFBTFDFOK-UHFFFAOYSA-N acetic acid;platinum Chemical compound [Pt].CC(O)=O ZDYCQQFBTFDFOK-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- MUMZUERVLWJKNR-UHFFFAOYSA-N oxoplatinum Chemical compound [Pt]=O MUMZUERVLWJKNR-UHFFFAOYSA-N 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 150000003376 silicon Chemical class 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 210000000498 stratum granulosum Anatomy 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000007704 wet chemistry method Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
- B01D53/944—Simultaneously removing carbon monoxide, hydrocarbons or carbon making use of oxidation catalysts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/652—Chromium, molybdenum or tungsten
- B01J23/6527—Tungsten
-
- B01J35/40—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/10—Noble metals or compounds thereof
- B01D2255/102—Platinum group metals
- B01D2255/1021—Platinum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/207—Transition metals
- B01D2255/20707—Titanium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/207—Transition metals
- B01D2255/20776—Tungsten
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/30—Silica
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/01—Engine exhaust gases
Abstract
The present invention relates to catalyst（10）, this catalyst preparation method, the application of this catalyst and the coating prepared with this catalyst, the catalyst particularly be used for oxidation gaseous effluent composition, such as nitrogen oxides, preferably nitric oxide, the wherein catalyst（10）By with platinum（20）, particularly platinum grain coating particle carrier material（30）Constitute, the carrier material（30）Derived from containing titanium nano particle, preferably titanium oxide nanoparticles, particularly titania nanoparticles.
Description
Technical field
The present invention relates to catalyst, the root particularly for oxidation gaseous effluent composition of preamble according to claim 1
The method and preamble according to claim 13 for being used to prepare this catalyst according to the preamble of claim 7
The application of above-mentioned catalyst and preamble according to claim 14 use the coating of this catalyst preparation.
Background technology
Catalyst, the particularly catalyst for oxidation gaseous effluent composition are known for a long time and widely made
With such as downstream in internal combustion engine, to remove undesirable exhaust gas constituents from the waste gas of internal combustion engine.
Here, the key molecule when reducing undesirable exhaust gas constituents is NO2。
To minimize carbon containing thin material grainses, in the car usually using so-called particle settler or particle filtering
Device.Typical particle precipitator device in the A2 of EP 1072765 in a kind of known automobile.This kind of particle settler and particle mistake
The difference of filter is to guide the waste gas stream along sedimentation structure, and the waste gas has to flow through filter medium in particulate filter.
Due to this difference, particulate filter is easy to block, which increase exhaust back-pressure, it means that causing engine exhaust gas outlet
Locate unacceptable pressure increase, this makes engine efficiency reduce and cause the high burnup of internal combustion engine again.In the A2 of EP 0341832
The example of known this kind of particulate filter arrangements.
In above two device, be arranged in the oxidation catalyst of particle settler or particulate filter upstream respectively by
In the residual oxygen (O also contained2) nitric oxide (NO) in waste gas is oxidized to nitrogen dioxide (NO2), and carry out as the following formula：
2 NO + O2 <-> 2 NO2 (1)
It should be noted that the balance of above-mentioned reaction is located at NO sides at high temperature.This is caused by thermodynamics and is limited in height again
Achievable NO under temperature2- share is limited.
The NO2Again CO, CO are generated in particulate filter with carbon containing thin material grainses reaction2、N2And NO.Therefore by means of
Strong oxidizer NO2The continuous removal of the thin material grainses of deposit is realized, thus can remove regeneration cycle from, and in other devices
The regeneration cycle must be carried out intricately.Referred to here as passive regeneration, it is carried out as the following formula：
C + 2 NO2 -> 2 NO+ CO2 (2)
NO2 + C -> NO + CO (3)
Here, according to equation（3）Formed carbon monoxide only serve unessential effect, in most cases occur with
The complete oxidation of the carbon of the form of carbon dioxide, until oxidation state+4, wherein needing two for the oxidation of each carbon molecules
Individual NO2Molecule.
Except NO2Outside, SO is also formed by the sulphur contained in fuel oil and/or machine oil in the NO- oxidation catalysts of platiniferous3.Should
SO3And NO2Cold spots in exhaust pipe condenses into the sulfuric acid and nitric acid of highly corrosive, therefore giving up until particulate filter
Device of air must be made of stainless steel, to avoid corrosion.
Aoxidize SO2Another problem is that due to sulfate and in the worst case because sulfuric acid is in the thing of catalyst surface
Reason is adsorbed and inactivates NO- oxidation catalysts
SO3 + H2O -> H2SO4
Common based on Al according to prior art2O3Catalyst on, the inactivation of catalyst can be by by EGT
It is increased to exceed 500 DEG C and again reverses it, but so high EGT is in the internal combustion engine of modern consumption optimization
Almost no longer occur.
If by NO2Do not make the carbon complete oxidation deposited in particulate filter, then carbon content increases and thus increased
Exhaust back-pressure is added.To avoid this situation, particulate filter is actually allowed to increase the catalyst coatings (EP for being configured to aoxidize NO
0341832 A2).Herein relate to the catalyst converter with platiniferous coating.But the known method the disadvantage is that, in particulate filter
The NO of middle formation2It only can be used to aoxidize the particle deposited in the downstream for the NO- catalytic active layers aoxidized, i.e., therefore in mistake
Particle in filter medium.If on the contrary, forming the stratum granulosum of deposit i.e. on filter surfaces and thus on catalytic active layer
So-called filter cake (Filterkuchen), then the NO- oxidation catalysts of the particulate filter side be located at the filter cake downstream so that
The carbon black pellet of there deposit should not be used to the NO from the NO- oxidation catalysts being applied on particulate filter2Aoxidized.To this
Can also precisely, the catalyst layer only applied on untreated gas side (Rohgasseit) contributes to the performance of the system, because
To be catalyzed the NO of formation on purified gas side2It is no longer able to connect with the carbon black deposited on untreated gas side and in filtering material
Touch.
The particulate filter coating another problem is that, the geometrical surface of the filter is significantly less than conventionally used
The surface area of catalyst converter base material.Its reason be the untreated gas side of the filter need larger free cross section and thus need compared with
Big free volume, to store carbon black-and machine oil ash.If using ceramic filter substrate, this can by 50 holes/square
Foot（cpsi）- 200 cpsi small hole density is realized.In contrast, pure catalyst converter is generally with 400 cpsi-900 cpsi
Hole density carry out.Make geometrical surface from 1 m by bringing up to 900 cpsi from 50 cpsi2/ l increases to 4 m2/ l, thus
It is greatly improved the conversion ratio of catalyst converter.
Thus reason, although the filter has catalyst coatings, can not abandon the NO- oxidation catalysis before particulate filter
Device, so that producing larger structural volume.This is even in the NO- oxidation catalyzers and particulate filter formation construction unit
It is such case, the entrance area of the wherein particulate filter is designed to NO- oxidation catalyzers, such as the institute in the A1 of DE 10327030
State.
All these by NO2It is noted that in the temperature less than 200-230 DEG C by carrying in the scheme of passive regeneration
High NO2Amount be also impossible to further improve carbon black oxidation.Conversion ratio maximum is reached at about 370 DEG C.From the temperature,
According to above-mentioned reaction（2）Carry out the oxidation of carbon black, i.e., two NO2Molecule and a carbon molecules are reacted.This means with data
For, with 1g NO20.13g carbon can be aoxidized；In other words, can be by improving NO2Amount arbitrarily improve the oxygen of carbon black
Change.
If temperature is less than 200-230 DEG C, the reliable function of particulate filter cannot ensure.This typically occurs in low negative
In the situation of load and with engine in the car, such as situation of passenger stock, bus and garbage truck, these are in addition
Also there is high idle running ratio.Therefore, second of possibility of particulate filter regeneration is especially used in these cases, that is, is led
EGT is improved dynamicly.Generally, this in the upstream of the upstream of catalyst, particularly HC oxidation catalysts by adding hydrocarbon（HC）
Come carry out.Because the hydrocarbon of addition by the oxidation of catalyst is heat release, realizes obvious temperature and rise；
"HC" + O2 -> CO + H2O (4)
"HC" + O2 -> CO2 + H2O (5)
In order that the enough thermostabilizations of these catalyst, it mostly contains palladium as active component.Palladium is although with very
Good HC- oxidation activities, but do not have NO- oxidation activities and reduce the NO- oxygen for the platinum that may be contained in catalyst in addition
Change activity.This causes HC oxidation catalysts to have significantly lower NO- oxidation activities than pure NO- oxidation catalysts.
Reach more than 600 DEG C of temperature by measuring addition hydrocarbon, this cause the carbon that is deposited in particulate filter by means of
Oxygen occurs oxidation or causes it to burn out, and it is carried out as the following formula：
C + O2 -> CO2 (6)
2C + O2 -> 2CO (7)
But, danger is there is in the so-called active filter regeneration, i.e., is burnt by the exothermicity of carbon containing carbon black
To the greatest extent strong temperature can be caused to raise, to 1000 DEG C of highest, and thus can cause particulate filter and/or the catalyst converter in downstream
It is impaired.Additionally due to temperature rise need to keep several minutes of quantitative oxidations to ensure carbon black pellet, so required hydrocarbon amount is not
It is insignificant, and this makes the deterioration of efficiency of internal combustion engine, because being used as hydrocarbon source usually using the fuel.
With passive regeneration on the contrary, another problem is that carbon monoxide emission high in regenerative process, it is formed in equation
（7）Described in.For this reason, it is necessary to another catalyst converter is installed on particulate filter and/or in particulate filter downstream
For aoxidizing the carbon monoxide formed in regenerative process, to avoid discharging it into environment.
It is not appropriate by adding hydrocarbon before NO- oxidation catalysts and simply closing passive and initiative regeneration：
Because temperature is increased to more than 600 DEG C, because thermodynamics limit value is almost no longer formed on NO- oxidation catalysts
NO2.Additionally due to substantial amounts of hydrocarbon and be suppressed NO oxidation, thus cause NO2Formation greatly reduce.This causes this
Grain must be aoxidized only by means of oxygen, because in this stage without NO2It is available for utilizing, this just extends the recovery time and caused high
Carbon monoxide emission.
Meanwhile, the NO- oxidation catalysts are more far short of what is expected than the catalyst converter for oxygenated hydrocarbon for the stability of pyrolytic damage, because
Occur the irreversible sintering of active component when temperature is higher than 550 DEG C, and NO- oxidation activities decline thus occur.
Except aoxidize the carbonaceous particles in particulate filter and in addition to, also using NO2To accelerate SCR to react（Selectivity is urged
Change reduction reaction）Or in NOxIt is used for forming nitrate in storage catalytic device.
As already mentioned above, it is the problem of NO- oxidation catalysts, it loses in the case where there is oxysulfide
Living, the oxysulfide is formed by the sulphur in burning fuel or lubricating oil.The possibility for reducing the problem is, uses
Titanium dioxide replaces being typically used as the Al of catalyst carrier material2O3：Three oxygen are adsorbed with much lower degree on the titanium dioxide
Change sulphur or sulfuric acid, while being desorbed at considerably lower temperature.But, using TiO2When problem appear to is that,
At higher temperature occur conversion of the anatase form to rutile form, this cause BET surface area reduction and therefore it is adjoint
The reduction of activity.
The further drawback of the method used at present is that this kind of known catalyst is prepared by wet chemical method, and this leads
Real active component platinum is caused often by Al2O3Carrier material is surrounded, and therefore cannot be used for actual reaction.
The content of the invention
It is an object of the present invention to be provided in the case where avoiding disadvantages mentioned above for oxidation gaseous effluent composition, particularly one
The catalyst of nitrogen oxide, relative to hitherto known catalyst, the catalyst is in terms of resistance to SO_2 and in terms of heat endurance
Improved, it is of the invention to also reside in the preparation method that this catalyst is provided, the application of this catalyst and with this catalysis
Coating prepared by agent.
The purpose by catalyst according to claim 1, the preparation method of this catalyst according to claim 7,
The application of this catalyst according to claim 13 and the coating according to claim 14 by using this catalyst preparation
And be achieved.
The purpose is especially by catalyst, particularly for oxidation gaseous effluent composition, such as nitrogen oxides, preferably one oxidation
The catalyst of nitrogen and be achieved, wherein the catalyst by with platinum, particularly platinum grain coat particle carrier material constitute,
The carrier material derives from the nano particle and/or preferred titanium oxide-nano particle of titaniferous, is particularly titanium dioxide-nanometer
Particle.
The present invention a basic point be that the catalyst is made up of granular carrier material, the carrier material by
The nano particle composition of titaniferous, wherein the titaniferous nano material platinum, particularly platinum grain coating.
Accordingly, with respect to catalyst known in the art, catalyst of the invention has two significant advantages, and this is excellent
Point is that the carrier material of the catalyst is made up of the nano particle there is provided very big surface area, and the nano material is used
Platinum grain, preferably Pt nanoparticle are coated, and they are the oxidation components for playing catalytic action of catalyst of the present invention.
Therefore, according to the present invention, the carrier material of catalyst of the invention is titanium-based, wherein the carrier material preferably by
Titanium oxide-nano particle and particularly preferably it is made up of titanium dioxide-nano particle, they have been catalytic action containing alloy platinum material
Carrier.According to the present invention, the metal platinum being arranged on containing alloy platinum material on carrier material particles surface.Here, the platinum
Grain is connected via contact area with carrier granular, the contact area can be formed as point-like to planar, and the platinum
The remaining surface of grain is then available for being used according to the catalysis of the present invention in very favorable mode, and there is no by on-catalytic
The titanium-containing materials covering of activity.By this way, on the one hand catalyst of the invention provides the maximum platinum for playing catalytic action
Surface, on a surface can with antioxidant nitroxide, particularly nitric oxide, in addition thus except maximum platinum surface and in addition to,
Very big catalyst made from platonic component surfaces of carrier materials disposed thereon is also provided in each carrier material particles,
Because the carrier material is made up of several nanometer scales and with sizable surface area very small nano particles.
Here, the preparation containing titanium nano particle according to prior art by the way that the precursor material of titaniferous is incorporated into flame or
Carried out in pyrolysis oven, as example described in the B4 of DE 101 09 892 or the B1 of EP 0 778 812.
Therefore, except very big catalytically active surface and in addition to, catalyst of the invention has another important advantage, its
In, the catalyst is because its titaniferous carrier material is for sulfur poisoning, i.e., it is extremely inert to be inactivated due to sulphur-containing substance, and
And also maintain its catalytic activity in the case of contaminated fuel of the burning with sulfur-containing compound.
According to one useful embodiment of the invention, substantial amounts of carrier material particles are by being arranged between these particles
, particularly containing metal oxide, preferably siliceous and/or tungstenic bridge is connected with each other.As the present invention found, by
These bridges between each carrier material particles, particularly titanium dioxide crystal make these titanium dioxide crystals in the form of anatase
It is stable, and hinder even to completely inhibit the conversion to rutile titanium dioxide generally more than 550 DEG C occurred, so that
According to substantially being arrived with the titanium dioxide crystal of anatase form for being connected with each other with siliceous and/or tungstenic bridge of the present invention
A maximum of about of 800 DEG C are all stable.This means another important advantages of the present invention, because the anatase form of titanium dioxide
There is provided the surface area much larger compared with its rutile form, thus the catalyst of the present invention catalyst surface area not only by shape
Into carrier material nano particle with its very big external surface area, also by the crystal structure of these titania nanoparticles
And produce.
In addition, preferred embodiment being provided according to the present invention is another, make the substantial amounts of carrier for coated particle shape
Between the platinum grain of material by be arranged in it is between these particles, particularly containing metal oxide, it is preferably siliceous and/or contain
The bridge of tungsten and be connected with each other.Make platinum stable by these bridges formed between platinum grain, and particularly reduce at high temperature or
Person preferably prevents it from sintering completely.
Herein it may be noted that the bridge being arranged between platinum grain and/or carrier material particles can be only present in carrier material
Expect between particle, or may reside between carrier material between platinum grain, and be optionally present in addition platinum grain and
Between carrier material particles.
Find that the bridging of platinum grain is although due to each contact point of each bridge in an advantageous manner according to the present invention
（Anlagepunkt）And caused the faint reduction on the platinum grain surface of catalytic activity effect, but by avoiding platinum in high temperature
Under sintering, the catalyst according to the invention loss of activity related to sintering be only very small.Therefore, catalyst of the present invention with
Its time course used and it is stabilized, and used with the very big surface for playing catalytic activity effect steady in a long-term
In oxidation gaseous effluent composition, particularly nitric oxide.
In addition, it has been found in accordance with this invention that can further make platinum thermostabilization by adding containing palladium compound in addition,
And therefore according to application field, catalyst of the invention can optionally contain palladium.
According to the present invention, the platinum concentration of the catalyst is in 0.5 mg -150mg/g catalyst weights, preferably in 1 mg
The scope of -100mg/g catalyst weights.Therefore, it can be provided with optimal for respective application field according to the present invention
Design is active and platinum consumes low catalyst simultaneously, and causes the cost pole for providing catalyst of the present invention by this way
It is economical.Here, scope of the platinum concentration specifically preferred according to the invention in 1 mg -80mg/g catalyst weights.Term catalyst
This refers to the gross weight of carrier material, alloy platinum material and bridge material for weight.As described above, being arranged in platinum grain and/or carrier material
The material of bridge between material particle is preferably siliceous（That is oxide containing silicon）And/or tungstenic, wherein here it is also preferred that tungsten
Oxide.The advantage containing silicon bridge between platinum grain and/or carrier material particles is, the oxidation activity of platinum is made peace because
This silicon for the oxidation reaction that nitric oxide generates nitrogen dioxide is inert.Therefore, if except the oxidation of nitrogen oxides
Outside reaction, SCR reactions be also it is desired, then according to it is contemplated by the invention that using tungstenic material be used to being formed platinum grain and/
Or the bridge between carrier material particles, because tungsten oxide is catalytic activity for SCR reactions, and it is particularly by this way
Contribute to remove nitric oxide in the way of being combined with the nitrogen dioxide that catalysis is produced.
In addition, the catalyst of the present invention has 20:1-2:1 titanium:Silicon ratio and/or 80:1-8:1 titanium:Tungsten ratio.With
Favourable mode, catalyst of the present invention can also be adapted to its respective application field by this way, either be set in burning
In standby, in garbage incinerating system, in gas turbine, in other industrial equipments burnt or in internal combustion engine.Example
Such as, when flow through and/or circulation cross catalyst waste gas it is colder when, then can reduce the silicone content in catalyst of the present invention, from
And cause the anatase form of titanium dioxide to the conversion of rutile form（In the Si oxide without titanium dioxide carrier material
Temperature in the case of stabilized more than 550 DEG C can just occur）Due to will not substantially occur than relatively low EGT.Cause
This, can be adapted to catalyst by the silicone content in raising catalyst of the present invention and occur in each case according to the present invention
EGT, respectively prepare the catalyst.
In addition, the purpose of the present invention is also realized especially through the preparation method of catalyst, the catalyst, which is particularly, to be used for
Oxidation gaseous effluent composition, such as nitrogen oxides, preferably nitric oxide, wherein being carried out according to the following steps：
- precursor material of titaniferous first is provided, for producing carrier material；
Second precursor material of-offer platiniferous, for component that produce catalytic activity, to be particularly oxidation；
- provide be particularly siliceous and/or tungstenic and/or the 3rd precursor material containing palladium, for produce stabilization material,
Particularly stabilize bridge；
- the first precursor material of titaniferous is incorporated into the reaction zone that can be through-flow of pyrolysis installation, such as flame or heat
Solve stove；
- be incorporated into the second precursor material of platiniferous in reaction zone in the downstream of the first precursor material of addition titaniferous；With
- be incorporated into the 3rd precursor material in reaction zone as follows：
- together with the introducing of the first precursor material of titaniferous simultaneously carry out and/or
- addition titaniferous the first precursor material downstream and/or
- in the downstream for the second precursor material for adding platiniferous.
One basic point of the inventive method is, in the reaction zone of pyrolysis installation, such as in flame or pyrolysis oven,
First, second, and third precursor material is sequentially reacted generation catalyst component, i.e., on the one hand generation carrier material,
On the other hand generation oxidation activity catalyst material and generate stabilization material in addition, the stabilization material make platinum grain with/
Or carrier material particles are connected with each other by bridge.
Can be with the reaction zone of through-flow pyrolysis installation therefore, each precursor material is incorporated on preferred flow direction
In, wherein term " downstream " and " upstream " hereinafter refer to the above-mentioned preferred direction of flow in operation used.
According to the present invention, new oxidation catalyst can be provided by the method for the present invention, according to application field, it has
There are suitable stability and simultaneously optimized catalyst activity.Therefore, according to the present invention can by the 3rd precursor material with
First precursor material of titaniferous is incorporated into the reaction zone of pyrolysis installation simultaneously, and the 3rd precursor material, which is used to produce, stabilizes material
Material, i.e., be particularly used to be formed to stabilize bridge.In this case, on the one hand formed by the first precursor material of titaniferous as new
The titanium oxide compound of the carrier material of type catalyst, i.e., preferred titania nanoparticles, and on the other hand before the 3rd
Body material, the bridge of oxidisability of particularly siliceous and/or tungstenic the 3rd precursor material formation between titan oxide particles.
According to the alternative plan of the inventive method, the 3rd precursor material can added the first precursor material of titaniferous
Downstream is added in reaction zone.It is preferred that such way, because by this way can be first by the first precursor material of titaniferous
Reaction generation titanium oxide, particularly generation titanium dioxide, thus in the second step, that is, exist in the reaction zone of pyrolysis installation
The 3rd precursor material for forming bridge is added in reaction zone by the downstream for adding the first precursor material of titaniferous.According to the present invention,
Can be avoided as much as by this way first and the 3rd precursor material mixing so that the 3rd precursor material is solely for
The bridge material formed between titanium oxide nanoparticles, and do not occur the mixing of Si oxide and titanium oxide substantially.
In the first scheme, i.e., by first and the 3rd precursor material simultaneously be incorporated into the reaction of pyrolysis installation, and
In the alternative plan, wherein downstream of the 3rd precursor material at the addition of the first precursor material of titaniferous is added,
The second precursor material of platiniferous is incorporated into the reaction zone of pyrolysis installation in downstream in another step, wherein introduced platinum
Compound and then reaction preferably generate metal platinum.
According to above-mentioned two methods scheme, by by the first precursor material of titaniferous and before forming the 3rd of bridge
Second precursor material of platiniferous is incorporated into reaction zone by the time point that body material is incorporated into the reaction zone of pyrolysis installation, it is ensured that
Platinum grain is deposited on the surface of carrier material particles, and the active surface of platinum grain is not formed carrier material or shape
Cheng Qiao material covering.Therefore, by adding the second precursor material of platiniferous in the downstream of the precursor material of addition first and the 3rd
It is added in reaction zone to avoid the limitation to catalyst activity, because the platinum of the catalyst with maximum useable surface area can be provided
Component is used for oxidation catalysis.
Can be brilliant with stabilized chlorine titanium by forming metal oxide bridge between each titanium dioxide granule or-crystal
The anatase form of body so as to titanium dioxide crystal rutile structure conversion without being the temperature more than 550 DEG C
Have occurred and that, but just occur at a temperature of higher than 800 DEG C.Therefore, by forming oxide between titanium dioxide granule
's（But it is not titanium oxide）Bridge can provide the anatase structured maximum surface area based on titanium dioxide crystal.
In addition, the third program of the method according to the invention can be by the second precursor material of platiniferous before the first of titaniferous
Downstream at the addition of body material is incorporated into the reaction zone of pyrolysis installation, the 3rd precursor material without will form bridge in advance
It is incorporated into reaction zone.In this case, formed to go out in titanium oxide crystal form by the first precursor material of titaniferous first
Existing titanium dioxide, the platinum grain then formed by the second precursor material in the reaction zone of pyrolysis installation is deposited on thereon.Root
According to the present invention, oxidation catalyst can be provided by this way is used for oxidation gaseous effluent composition, such as nitrogen oxides, preferably one oxidation
Nitrogen, it with carrier material that form of nanoparticles is present with very big surfaces of carrier materials due to being accumulated, in cloth again thereon
The metal platinum of Nanoparticulate is equipped with, the metal platinum is only used in each contact between platinum and titanium dioxide crystal for it
Position is connected with the latter, and provides maximum active catalyst surface area by this way.
In addition, according to same design of the present invention, the carrier material of platinum is will be covered with a subsequent step
Grain is exposed to the 3rd carrier material, and the 3rd precursor material is incorporated into pyrolysis dress in the downstream of the second precursor material of addition platiniferous
React in the reaction zone put and there, and on the one hand between titanium dioxide nano-crystal and on the other hand platinum grain it
Between form bridge, the advantage is that, the oxidation that one side titanium dioxide crystal is formed with anatase form by the 3rd precursor material
Thing bridge is stable, and another aspect and the sintering for preventing platinum also by the bridge of the containing metal oxide between platinum grain in addition, from
And platinum grain is maintained, the particularly big surface area of Pt nanoparticle.As described above, titanium dioxide crystal and/or being arranged in
The stabilisation of platinum to what extent on carrier granular is necessary or desired, uses neck depending on respective herein
Domain, wherein the degree formed by respective bridge and the amount of the 3rd carrier material each added can subtly adjust the present invention
The desired requirement in each case of novel oxidized catalyst.
The precursor material specifically preferred according to the invention being used alone or in combination can be obtained from following table：
Need herein it is further noted that palladium compound can also be used, particularly palladium chloride, preferably with silicon compound
And/or tungsten compound is combined as the 3rd precursor material.According to the present invention, silicon compound and/or tungsten compound are herein used as
The precursor material of bridge is formed, and palladium compound is used for making NO- oxidation catalysts have high HC- oxidation activities, without making NO-
Oxidation activity is reduced due to the covering of palladium.
But, if purpose is thermally-stabilised platinum and the sintering for preventing platinum crystal, it regard palladium and platinum as the second precursor material
Add together, be consequently formed platinum-palladium compound.However, due to covering platinum surface by palladium, NO- oxidation activities by this method
Decrease, but this HC- oxidability but to catalyst plays positive role.
In the reaction zone of pyrolysis installation, react the first precursor material being substantially made up of titanium compound, so that by
Used titanium compound formation titanium oxide, preferably titanium dioxide.
Equally, this is also applied for the precursor used according to the invention in the case of silicon compound and/or tungsten compound
Material, it also reacts or aoxidized the respective oxide of generation, particularly silica and tungstic acid respect to which.
As a result of which, by it is described so long as not palladium compound first and/or the 3rd precursor material in oxidisability gas
It is introduced together into atmosphere or substantially with oxidizing atmosphere in the reaction zone of pyrolysis installation.Gaseous oxygen is particularly by addition
Agent, such as oxygen, air or carbon monoxide produce oxidizing atmosphere in the reaction region.This is represented, just to reaction zone
Middle addition first and/or the 3rd before precursor material, simultaneously or after immediately, i.e., first and/or the 3rd precursor material each
Point of addition, corresponding particularly excessive oxidant is added equally into reaction zone, so that in the reactor first
And/or the 3rd precursor material be almost oxidized agent and surround, and directly contacted with oxidant so that can be formed it is corresponding before
The oxide of body material.
In addition, being devised according to the present invention, by second precursor material in reducing atmosphere or substantially with going back
Originality atmosphere is introduced together into reaction zone, wherein being particularly gaseous reducing agent by addition, such as hydrogen is produced in the reaction region
Raw reducing atmosphere.Here can also just add the second precursor material before, simultaneously or after immediately its add position
Put and reducing agent is introduced into reaction zone, so as to also ensure that the second precursor material is in close contact with reducing agent herein, can occur also
Original reaction, and be for example almost reduced agent encirclement or wrap.
Herein it may be noted that can also be by palladium compound in reducing atmosphere or substantially together with reducing atmosphere
It is incorporated into reaction zone, so that as the platinum compounds as being used as the second precursor material, in the reaction of pyrolysis installation
Respective metal is also formd by palladium compound in area.
In addition, the purpose of the present invention is realized by using according to above-mentioned catalyst, the catalyst is used to particularly exist
The downstream oxidation exhaust gas constituents of internal combustion engine, such as engine, particularly motor car engine, preferably such as nitrogen oxides, an oxygen
Change nitrogen.
In addition, coating of the purpose of the present invention also by particularly exhaust device, is especially consequently exerted at ceramics or metal
Coating in catalyst substrate and realize, the coating is prepared using according to above-mentioned catalyst.
With the therefore, it can summing-up following basic sides for summarizing the present invention：
Therefore, at least three kinds metallic compounds are introduced into solution according to the present invention, and are ejected into flame or pyrolysis oven
In.Wherein, a kind of metallic compound contains titanium and another containing platinum.3rd metallic compound is used for stable in pyrolysis installation
In, the particularly nanocrystal that is formed in flame.This can for example be carried out by using siliceous or tungstenic compound.
Therefore, three kinds of metallic compounds have following task：
1. titanium：Surface and carrier material are provided
2. platinum：Oxidizing component is provided
3. the 3rd metallic compound：Stable platinum, titanium dioxide or both.
The preparation of the nano particle of nanocrystal, particularly titaniferous is prior art, and as described above, by that will contain
The solution of titanium is ejected into flame or pyrolysis oven and realized, for example this in DE69509396T2 or DE10109892B4
Description.
The difference of method and mentioned prior art of the present invention is, in the downstream of introducing titanium-containing compound by platinum
Compound is ejected into flame or pyrolysis oven.
The advantage of this way is that platinum is deposited on the surface of titanium oxide crystal.With washing for common wet chemistry method
Apply（Washcoat）Synthesis thus without by inactive titanium dioxide on the contrary, cover, and therefore protected in use below
Holding NO molecules can freely approach.
In addition, the above-mentioned catalyst basic material being made up of titanium dioxide and platinum is stablized by another metal oxide,
Equally the metal oxide is added in flame or pyrolysis oven.Advantageously, it is tungstenic and/or siliceous compound.
There is the possibility of plurality of stable herein：
Because add titaniferous into flame simultaneously and stability is siliceous or metallic compound of tungstenic, by each sharp
Between the titanium dioxide crystal of titanium ore form formed metal oxide but the bridge of titanium-containing oxide does not carry out stabilized chlorine titanium.By
This can make titanium dioxide until heat is still stablized to about 800 DEG C, and usually above 550 DEG C, titanium dioxide can turn higher than 550 DEG C
It is melted into rutile-type.If adding stability metal compound into flame or pyrolysis oven in the downstream of the compound of addition titaniferous
Thing, then can improve the formation of bridge in addition, because titanium dioxide nano-crystal has been formed herein, and stability metallizes
Compound is deposited on these surfaces in which can be particularly suitable for.
If in addition addition compound containing platinum downstream add these stability metallic compounds, in addition platiniferous with
Bridge containing the containing metal oxide that stability is formed between titanium crystal, these bridges stabilize platinum and prevent it to sinter in addition.
But, it is assumed that the disadvantage is that, in subregion platinum crystal may by stability containing metal oxide compound cover,
This how many activity for reducing catalyst in theory；But this is partly compensated by avoiding the sintering of platinum.In order to keep away
Exempt from these, compound of the stability containing metal can also be added between the solution of platiniferous in addition titaniferous.
TiCl can be used as the precursor of titanium-containing compound4、Ti(NO3)2, Titanium alkoxides, titanium acetate, tetraisopropoxide
Titanium or Ti (SO4)2.SiCI can be used as the precursor of stability compound4Or silane, particularly HMDO,
And WBr3、WCl3, tungsten acetate, tungsten alkoxide, nitric acid tungsten or tungstates, such as (NH4)10W12O41。
As the precursor of compound containing platinum can use platinum chloride, acetic acid platinum, four ammino platinic hydroxides, platinum alkoxide or
Platinum nitrate.
Also to make platinum further thermally-stabilised, containing palladium compound can also be added.
To ensure the precursor containing metal being oxidized to metal oxide, what is shared is to additionally introduce oxidation in the reaction region
Agent, such as oxygen, air or carbon monoxide.Again may be by adding reducing agent such as hydrogen optimize platinum and palladium compound also
It is former.
Other embodiments of the present invention are obtained in dependent claims.
Brief description of the drawings
The present invention is described below by way of embodiment, and the accompanying drawing being previously mentioned is expanded on further.Wherein：
Fig. 1 shows the schematic diagram of catalyst according to the first embodiment of the invention；
Fig. 2 shows the schematic diagram of catalyst second embodiment of the invention；
Fig. 3 is shown to be used to prepare showing for catalyst reaction process of the invention according to embodiment shown in figure 2
Example property schematic diagram；With
Fig. 4 shows the illustrative diagram of the construction for preparing catalyst according to the invention.
Embodiment
In the following description, the part for identical or phase same-action has used same reference numeral.
Fig. 1 shows the schematic diagram of catalyst of the present invention according to the first embodiment of the invention, wherein titanium dioxide
Particle is used as carrier material in the form of anatase（30）.The carrier material of titania nanoparticles derived from anatase form
Particle（30）Pass through siliceous, i.e. silica containing bridge（40）It is connected with each other, and is stabilized to rutile titania by this way
The form of ore deposit.In carrier material particles（30）On remaining surface.Arranged i.e. on the surface without bridging in the form of platinum grain
There is platinum crystal（20）.If in stability precursor（Precursor 3）And titanium-containing precursors（Precursor 1）Downstream the precursor of platiniferous is added respectively
In the flame or pyrolysis oven that are added in respective reaction zone, then the first embodiment of the present invention is obtained.
In contrast, Fig. 2 shows second embodiment of the present invention in the diagram, wherein not only by anatase structured
Titanium dioxide nano-crystal formation carrier material（30）And it is arranged in the carrier material particles（30）On platinum grain
（20）Connected by the bridge derived from Si oxide.If in the downstream of titaniferous and the premise of platiniferous by stability silicide-comprising
Compound is added in the reaction zone of pyrolysis installation, i.e., in flame or pyrolysis oven, then obtains this reality of the catalyst of the present invention
Apply mode.
Fig. 3 shows such mode of operation in the diagram.Here, first by the first precursor material of titaniferous（31）Spray
It is mapped in the flame of pyrolysis installation, and then in the first precursor material of initial titaniferous（31）Addition at downstream by platiniferous
The second precursor material（21）It is ejected into flame.By the first precursor material of titaniferous（31）With the second precursor material of platiniferous
（21）After being ejected into flame, then downstream again at both initial additions will form the 3rd precursor material of bridge
（41）It is added in flame.According to this embodiment, the first precursor material of titaniferous（31）Addition be oxygen excess area carry out
So that the precursor compound of titaniferous reaction generation titanium dioxide in pyrolysis flame.In the precursor material of titaniferous（31）'s
With the second precursor material at addition（21）Into the flame of pyrolysis installation, hydrogen is added in metering simultaneously together（It is not shown）, and
3rd precursor material（41）Addition at region in again be that there is excessive oxygen, this is by adding air（It is not shown）Come
Set up.
Fig. 4 schematically shows the preparation of the catalyst of the present invention according to Fig. 1.Here, it is transmitted by oil bath temperature adjustment
Oxygen is imported to 98 DEG C of wash bottles, contains tetraisopropoxy titanium in the wash bottle（TTIP, 98%）31, flow is 7.5 l/min.Via
It is heated to the center that the carrier streams containing tetraisopropoxy titanium are transported to burner 44 by 220 DEG C of conduit.In the conveying
Side introduces the methane and oxygen as fuel gas.In flame of its formation, streamwise first is by SiCl4It is water-soluble
Liquid 41 is via O2- air-flow（7.5 l/min）Input, and and then by PtCl4The aqueous solution 21 is inputted via hydrogen carrier stream.
The hydrogen carrier stream ensure that reducing atmosphere in the reaction region, so as to form platinum crystal rather than with substantially low
The platinum oxide crystal of NO- oxidation activities.What is be connected with this is that area 46 is quenched, and makes reaction temperature by means of the air of input wherein
Degree is suddenly reduced, and therefore avoids flocculation.Finally, the gas transport flowed out from reactor is via filter 45
Export, separates resulting catalyst and air-flow by the filter.
Table below shows compared to corresponding to prior art so far based on Al2O3Catalyst obtain
NO2/NOxThan the catalyst according to the invention obtained with the method catalysis for showing and being carried out by Model gas units in Fig. 4
NO2/NOxThan.For both catalyst, platinum carrying capacity is 9 mg/g, and space velocity is 40000 l/h and catalyst
Preceding NO concentration is 1000 ppm.For the catalyst of the present invention, the ratio of titanium and silicon is 15:1.As a result show, in the present invention
NO of the downstream of catalyst in all nitrogen oxides2- content is considerably higher, and therefore shows in more preferable catalyst performance
While reduce platinum amount and/or required catalyst volume potentiality.
* Pt dispersion rates are measured by CO chemisorbeds (referring to J. Anderson et al., Supported metals
In catalysts, Imperial College Press London 2005).
Herein it may be noted that all above-mentioned parts individually from the point of view of or in any combination of form, particularly attached
The details described in figure, is accordingly to be regarded as the essential and claimed of the present invention.Change by its progress is those skilled in the art institute
It is known.
Mark list：
10 catalyst
20 platinum grains
21 second precursor materials
30 carrier materials
31 first precursor materials
40 bridges
41 the 3rd precursor materials
45 filters
46 are quenched area
50 reaction zones
Claims (47)
1. catalyst（10）, it is used for oxidation gaseous effluent composition, it is characterised in that the catalyst（10）Comprising using platinum grain（20）Apply
The particle carrier material covered（30）, the carrier material（30）Derived from containing titanium nano particle,
Wherein substantial amounts of platinum grain（20）And/or containing titanium nano particle（30）It is intergranular containing metal oxidation via these are arranged in
The bridge of thing（40）It is connected with each other, wherein the bridge of the containing metal oxide（40）It is siliceous and/or tungstenic bridge.
2. catalyst according to claim 1（10）, it is characterised in that the exhaust gas constituents be the waste gas with nitrogen oxides into
Point.
3. catalyst according to claim 2（10）, it is characterised in that the nitrogen oxides is nitric oxide.
4. catalyst according to claim 1（10）, it is characterised in that it is described to contain titanium nano particle（30）It is titanium oxide-receive
Rice grain.
5. catalyst according to claim 4（10）, it is characterised in that the titanium oxide-nano particle is titanium dioxide-is received
Rice grain.
6. according to one of claim 1-5 catalyst, it is characterised in that the platinum grain（20）It is Pt nanoparticle.
7. according to one of claim 1-5 catalyst, it is characterised in that the catalyst（10）With palladium.
8. according to one of claim 1-5 catalyst, it is characterised in that the catalyst has urges in 0.5mg-150mg/g
The platinum concentration of agent weight range.
9. catalyst according to claim 8, it is characterised in that the catalyst has in 1mg-100mg/g catalyst weights
The platinum concentration of scope.
10. according to one of claim 1-5 catalyst, it is characterised in that the catalyst has 20:1-2:1 titanium:Silicon ratio
Example and/or 80:1- 8:1 titanium:Tungsten ratio.
11. catalyst（10）Preparation method, it is characterised in that the following steps：
First precursor material of-offer titaniferous（31）, for producing carrier material（30）；
- platiniferous and/or the second precursor material containing palladium are provided（21）, the component for producing catalytic activity；
- siliceous and/or tungstenic metal the 3rd precursor material is provided（41）, for producing stable bridge（40）；
- by the first precursor material of titaniferous（31）It is incorporated into the reaction zone that can be through-flow of pyrolysis installation（50）In；
- by the second precursor material of platiniferous（21）In the first precursor material of addition titaniferous（31）Downstream be incorporated into reaction zone
（50）In；With
- by the 3rd precursor material（41）It is incorporated into reaction zone as follows（50）In：
- the first precursor material with titaniferous（31）Introducing together simultaneously carry out and/or
- in the first precursor material of addition titaniferous（31）Downstream and/or
- in the second precursor material of addition platiniferous（21）Downstream.
12. method according to claim 11, it is characterised in that the catalyst (10) is to be used for oxidation gaseous effluent composition.
13. method according to claim 12, it is characterised in that the exhaust gas constituents are nitrogen oxides.
14. method according to claim 13, it is characterised in that the nitrogen oxides is nitric oxide.
15. method according to claim 11, it is characterised in that second precursor material（21）It is the material of platinum metal.
16. method according to claim 11, it is characterised in that the component of the catalytic activity has been the component of oxidation.
17. method according to claim 11, it is characterised in that the reaction zone that can be through-flow（50）It is flame or pyrolysis
Stove.
18. according to one of claim 11-17 method, it is characterised in that
Following material is used as precursor material either alone or in combination：
First precursor material：Titanium compound；
Second precursor material：Platinum compounds；Palladium compound；
3rd precursor material：Silicon compound；Tungsten compound.
19. method according to claim 18, it is characterised in that the material is used as precursor material as a solution.
20. method according to claim 18, it is characterised in that described titanium compound is titanium halogen compound and Ti (NO3)2、Ti
(SO4)2, titanium acetate, tetraisopropoxy titanium, Titanium alkoxides.
21. method according to claim 20, it is characterised in that the titanium halogen compound is TiCl4。
22. method according to claim 20, it is characterised in that the Titanium alkoxides are titanium tetraethoxides.
23. method according to claim 22, it is characterised in that the platinum compounds is platinum chloride, platinum acetate, four amminos
Platinic hydroxide, platinum alkoxide, platinum nitrate.
24. method according to claim 18, it is characterised in that the palladium compound is palladium chloride.
25. method according to claim 18, it is characterised in that the silicon compound is silicon halide, silane, silicon alkoxide.
26. method according to claim 25, it is characterised in that the silicon halide is silicon chloride.
27. method according to claim 26, it is characterised in that the silicon chloride is SiCl4。
28. method according to claim 25, it is characterised in that the silane is HMDO.
29. method according to claim 18, it is characterised in that the tungsten compound be tungsten halogen compound, tungstates, tungsten alkoxide,
Tungsten acetate, nitric acid tungsten.
30. method according to claim 29, it is characterised in that the tungsten halogen compound is WCl3、WBr3。
31. method according to claim 29, it is characterised in that the tungstates is (NH4)10W12O41。
32. according to the method for one of the claims 11 to 17, it is characterised in that by so long as not described the of palladium compound
One and/or the 3rd precursor material is introduced together into reaction zone in oxidizing atmosphere or substantially with oxidizing atmosphere（50）
In.
33. according to the method for claim 32, it is characterised in that in the reaction zone（50）In by add oxidant produce oxygen
The property changed atmosphere.
34. according to the method for claim 33, it is characterised in that the oxidant is gaseous oxidant.
35. according to the method for claim 34, it is characterised in that the gaseous oxidant is oxygen and/or air.
36. according to the method for one of the claims 11 to 17, it is characterised in that by second precursor material in reproducibility
Reaction zone is introduced together into atmosphere or substantially with reducing atmosphere（50）In.
37. according to the method for claim 36, it is characterised in that
In the reaction zone（50）In by add reducing agent produce reducing atmosphere.
38. according to the method for claim 37, it is characterised in that the reducing agent is gaseous reducing agent.
39. according to the method for claim 38, it is characterised in that the gaseous reducing agent is hydrogen and/or methane.
40. according to the catalyst of one of claim 1 to 10（10）Application, it is used for oxidation gaseous effluent composition.
41. according to the application of claim 40, wherein the exhaust gas constituents are nitrogen oxides.
42. according to the application of claim 41, wherein the nitrogen oxides is nitric oxide.
43. according to the application of claim 40, it is used for oxidation gaseous effluent composition in the downstream of internal combustion engine.
44. according to the application of claim 43, it is used for oxidation gaseous effluent composition in the downstream of engine.
45. according to the application of claim 44, it is used for oxidation gaseous effluent composition in the downstream of motor car engine.
46. coating, it uses the catalyst according to one of claim 1 to 10（10）To prepare.
47. according to the coating of claim 46, it is used to be applied to ceramics or metallic catalyst substrate.
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| DE102012013288.3A DE102012013288A1 (en) | 2012-07-05 | 2012-07-05 | Catalyst, process for the preparation of the catalyst, use of the catalyst |
| DE102012013288.3 | 2012-07-05 |
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| US (1) | US9067197B2 (en) |
| EP (1) | EP2682184B1 (en) |
| CN (1) | CN103521219B (en) |
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| US10201804B2 (en) * | 2015-01-29 | 2019-02-12 | Basf Corporation | Platinum group metal (PGM) catalysts for automotive emissions treatment |
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| WO2016154429A1 (en) * | 2015-03-24 | 2016-09-29 | Tecogen Inc. | Poison-resistant catalyst and systems containing same |
| CN108889297B (en) * | 2018-07-31 | 2020-12-29 | 包头稀土研究院 | SCR catalyst and preparation method and application thereof |
| US11802692B2 (en) * | 2020-04-17 | 2023-10-31 | Ut-Battelle, Llc | Monolithic gas trap adsorber for high efficiency, cost effective, low-emission condensing furnace |
| KR20220014120A (en) * | 2020-07-28 | 2022-02-04 | 현대자동차주식회사 | Catalyst for preparing synthesis gas, method for preparing the same, and method for preparing synthesis gas using the same |
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